Thin-film type sulfonation process

ABSTRACT

A process for thin-film type sulfonation of a sulfonatable reactant such as olefins and higher alcohols, which comprises adding a small amount of non-ionic surface active agent to said reactant and effecting sulfonation of said reactant in the presence of said surface active agent.

United States Patent [191 Kitano et al.

[ Feb. 4, 1975 [30] Foreign Application Priority Data Apr. 28, 1972 Japan 47-42794 [52] US. Cl. 260/459, 260/513 R [51] Int. Cl. C07c 139/00, C07c 143/06 [58] Field of Search 260/456 R, 459, 513 R [56] References Cited UNITED STATES PATENTS 3,084,176 4/1963 Dieckemam et al. 260/456 R 3,350,428 10/1967 Brooks et al 260/456 R 3,492,239 1/1970 Baumann et a1... 260/513 R 3,551,460 12/1970 Sowerby 260/459 R 3,763,208 10/1973 Sowerby 260/459 R Primary Examiner-Bernard Helfin Assistant Examiner-Norman P. Morgenstern Attorney, Agent, or Firm-Woodhams, Blanchard and Flynn [57] ABSTRACT A process for thin-film type sulfonation of a sulfonatable reactant such as olefins and higher alcohols, which comprises adding a small amount of non-ionic surface active agent to said reactant and effecting sulfonation of said reactant in the presence of said surface active agent.

5 Claims, No Drawings THIN-FILM TYPE SULFONATION PROCESS BACKGROUND OF THE INVENTION For the purpose of sulfonating olefins and higher alcohols usable as the raw material for surface active agents employment of the thinfilm type sulfonation process is popular. As is commonly known, this thinfilm type sulfonation process is intended to bring an olefin or a higher alcohol in the state of a thin film into contact with diluted S0,, gas. Generally speaking. the sulfonation reaction of an olefin or a higher alcohol with 80,, gas is defective in that, because the reaction speed is too fast and considerable heat is generated, it is difficult to control the reaction appropriately, and as a result, the color tone of the reaction product is very apt to deteriorate. Besides, when the substance to be sulfonated is an olefin, the yield of the intended monosulfonate is decreased due to generation of byproducts such as disulfanates. Such a tendency is present also in the thin-film type sulfonation process. Further, in the case of the thin-film type sulfonation process, there arises a problem that a portion of the product solidifies and adheres to the wall surface along which the thin film of olefin or higher alcohol flows, thereby impairing the cooling effect thereof. Besides, because the flow of the thin film is apt to become wavy, there also arises the trouble that generation of mist by the flow of diluted 50;, gas is inevitable.

The present invention is intended to overcome the foregoing drawbacks of the thin-film type sulfonation process by adding, prior to sulfonation a small amount of a non-ionic surface active agent to the olefin or a higher alcohol to be sulfonated.

SUMMARY OF THE INVENTION The present invention provides an improved thin-film type sulfonation process which is characterized by incorporating 30 10,000 ppm (by weight) of a nonionic surface active agent in the olefin or higher alcohol prior to sulfonating said olefin or higher alcohol by the thin-film type sulfonation process.

The process according to the present invention makes it possible to control the generation of byproducts incident to the thin-film type sulfonation process, to increase the yield of monosulfonate, to remarkably improve the color tone of the reaction products, and to further check the generation ofmist. The reason why such excellent effects ofthe present invention can be brought about may be explained as follows. To begin with, the non-ionic surface active agent employed in the present invention has the effect of slowing down the reaction rate of sulfonation reaction. In other words, when an olefin or a higher alcohol forms a flowing thin film, said non-ionic surface active agent present therein is concentrated centering on the surface of the flowing thin film coming in contact with the diluted S gas that is, the gas-liquid contact surface thereby obstructing the contact between the olefin or higher alco hol and 50;, to some extent. As a result, the rate of the sulfonation reaction is somewhat slowed down, and accordingly, an excessive sulfonation seems to be checked. The non-ionic surface active agent according to the present invention also has the effect of decreasing the gas-liquid contact surface area. In other words, according to the conventional thin-film type sulfonation process, the flow of thin film per se becomes a turbulent undulating flow having influence on the gasliquid contact surface too, and this causes not only the generation of mist but also an excessive sulfonation. While, according to the process according to the present invention, inasmuch as the non-ionic surface active agent works to drastically control the generation of undulating flow of the thin film to thereby decrease the gas-liquid contact surface, the generation of mist is minimized and the flow of thin film is improved to be of uniform thickness so that the cooling effect on said gas-liquid contact surface can be enhanced. Accordingly, the deterioration of the color tone of the prod ucts ascribablc to excessive sulfonation and the generation of byproducts such as disulfonates can be controlled. Moreover, the non-ionic surface active agent employed in the present invention displays the effect of preventing adhesion of solids on the wall surface along which the thin film flows. Considering that the adhesion of solids on the wall surface constitutes a cause for the generation of extremely pulsatile flow, this effect of preventing adhesion of solids is considered contribute to the prevention of the generation of mist and the control of excessive sulfonation.

The substances illustrative of the non-ionic surface active agent to be incorporated in the olefin or higher alcohol prior to sulfonation according to the process of the present invention, includes adducts of higher alcohol, alkyl phenol, fatty acid, fatty acid amide, etc. to ethylene oxide or propylene oxide; fatty acid diethanol amide; glycerol ester of fatty acid; fatty acid ester of sorbitan, sorbitol or sucrose; etc. The amount of these non-ionic surface active agents to be incorporated in said olefin or higher alcohol is usually in the range of 30 l0,000 ppm (by weight) preferably about 50 5,000 ppm (by weight) when it is less than 30 ppm, the aforesaid effect of the non-ionic surface active agent will not be displayed sufficiently, while any increase of said effect will be infeasible when it is in excess of 10,000 ppm.

The thin-film type sulfonation process according to the present invention renders it possible to sulfonate olefins having 12 22 carbon atoms and higher alcohols having 8 22 carbon atoms under substantially the same conditions as those employed in the conventional thin-film type sulfonation process. In this connection, as the conditions for practicing the conventional thinfilm type sulfonation process, the following conditions are generally adopted: the concentration of gas is in the range of about I 8 vol. 70, the molar ratio of S0,, (relative to olefin or higher alcohol) is in the range of about 0.8 1.30, the reaction temperature in the range of about 30 60 C and the length of the flow of thin film is in the range of about 0.5 3m. Besides, as to the aftertreatment of the sulfonation reaction product, the process according to the present invention does not differ from the conventional process, and the product can be subjected to such treatments as adjustment ofpH and bleaching, as occasion demands, subsequent to neutralization and hydrolysis.

DESCRIPTION OF THE PREFERRED EMBODIMENTS EXAMPLE I Upon adding Span 20 (the trade name of a manufacture of TOKYO KASEl K.K.) as the non-ionic surface active agent to a'olefin having l4 carbon atoms, sulfonation was effected by a thin-film type sulfonation process under the conditions of a in concentration of S0 gas 4 vol. 7c, a molar ratio of S0,, (relative to olefin of wh i l i d i 1.15) and a reaction temperature of 32 50 C. The 1. In a process for effecting the thin film sulfonation properties of the sulfonation reaction product in this Of Organic Sulfonateable material, in which a feed case were as shown i Tabl 1 b l stream of organic material isflowed in the form of a Table 1 Amount of Color tone Unreacted oil Byproduct surface active Transmittancy in content (petrodisulfonate agent employed 420 m (10 mm-cell) of 57: leum ether frac- (based on (ppm by wt.) aqueous solution of tion relative to active salt) olefin sulfonate active salt) (wt.'7z)

EXAMPLE 2 thin film along a reaction surface having a length of about 0.5 to 3 meters, and is contacted with a gaseous Except for substituting the adduct of 3 mols of ethyll lll and men gas wherem the concentra' 'de to laur 1 alcohol for the non-ionic surface actlon m the rangeabout l to 8 VOL and the reacene y tron temperature IS in the range of about to 60 C,

tive agent, the same thin-film sulfonation process as in the improvement which comprises: Exifmple l performefl- Propertles of the employing as the feedstream a mixture consisting esnation reaction product in this case were as shown in i u f 1 a lf t bl material Selected Table 2 behwf et.ths r aias s s of e nshay ns. 12 to 22 Table 2 Amount of Color tone Unreacted oil Byproduct surface active Transmittancy content (petrodisulfonate agent employed in 420 mp. (l0 mm'cell) leum ether (based on) (ppm by wt.) of 5% aqueous solution fraction relaactive salt) of olefin sulfonate tive to active (wt/7c) salt) (wt.

none 0.090 3.3 l5.0 30 0.045 3.0 l2.0 0.040 2.) H0 l00 0.035 2.9 l0.2 500 0.030 2.8 l0.0 1,000 0.027 2.6 9.9 5,000 0.025 2.7 10.2 10.000 0.027 2.5 10.2

EXAMPLE 3 carbon atoms and fatty alcohols having 8 to 22 carbon atoms, and (2) from 30 to 10,000 ppm by weight, based on the weight of l of a non-ionic Upon adding the adduct of 8 mols of ethylene oxide surface active agent selected from the group conto nonyl phenol to a synthetic alcohol hav ng l2 I8 50 sisting of(a) ethylene oxide or propylene oxide adcarbon atoms, thethln-tilm type sulfonatton process ducts of higher fatty alcohols, alkylphenols, fatty was performed under the same conditions as those in acids and fatty acid amides, (b) fatty acids die- Example 1. The properties of the sulfonatlon reaction thanolamides and (c) fatty acid esters of glycerol, P u In b isa s ews,39%-).RT3P1? ibs wn. b tq n o e,

Table 3 Amount of Color tone Unreacted oil content surface active (Transmittancy in (petroleum ether agent employed accordance with Tables 1 & 2) extraction based on (ppm by wt.) active salt) (wt/7:)

none 0.068 3.6 30 0.047 3.4 50 0.045 3.3 0.045 3.3 500 0.042 3.2 1,000 0.042 3.1 5.000 0.040 3.3 3.2

C14 a-olefin and (2) is an adduct of 3 mols olethylene oxide to lauryl alcohol.

5. A process according to claim 1, in which l is an alcohol having 12 to 18 carbon atoms and (2) is an adduct of 8 mols of ethylene oxide to nonyl phenol. 

1. IN A PROCESS FOR EFFECTING THE THIN FILM SULFONATION OF ORGANIC SULFONATEABLE MATERIAL, IN WHICH A FEED STREAM OF ORGANIC MATERIAL IS FLOWED IN THE FORM OF A THIN FILM ALONG A REACTION SURFACE HAVING A LENGTH OF ABOUT 0.5 TO 3 METERS, AND IS CONTACTED WITH A GASEOUS STREAM OF SO3 AND INERT GAS WHEREIN THE SO3 CONCENTRATION IS IN THE RANGE OF ABOUT 1 TO 8 VOL. %, AND THE REACTION TEMPERATURE IS IN THE RANGE OF ABOUT 30* TO 60*C, THE IMPROVEMENT WHICH COMPRISES: EMPLOYING AS THE FEEDSTREAM A MIXTURE CONSISTING ESSENTIALLY OF (1) A SULFONATABLE MATERIAL SELECTED FROM THE GROUP CONSISTING OF OLEFINS HAVING 12 TO 22 CARBON ATOMS AND FATTY ALCOHOLS HAVING 8 TO 22 CARBON ATOMS, AND (2) FROM 30 TO 10,000 PPM BY WEIGHT, BASED ON THE WEIGHT OF (1), OF A NON-IONIC SURFACE ACTIVE AGENT SELECTED FROM THE GROUP CONSISTING OF (A) ETHYLENE OXIDE OR PROPYLENE OXIDE ADDUCTS OF HIGHER FATTY ALCOHOLS, ALKYLPHENOLS, FATTY ACIDS AND FATTY ACID AMIDES, (B) FATTY ACIDS DIETHANOLAMIDES AND (C) FATTY ACID ESTERS OF GLYCEROL, SORBITAN, SORBITOL AND SUCROSE.
 2. An improved process according to claim 1, in which said non-ionic surface active agent is added to said reactant in an amount of from 50 to 5,000 ppm.
 3. A process according to claim 1, in which (1) is a C14 Alpha -olefin and (2) is a fatty acid ester of sorbitan.
 4. A process according to claim 1, in which (1) is a C14 Alpha -olefin and (2) is an adduct of 3 mols of ethylene oxide to lauryl alcohol.
 5. A process according to claim 1, in which (1) is an alcohol having 12 to 18 carbon atoms and (2) is an adduct of 8 mols of ethylene oxide to nonyl phenol. 